N-bis(2-benzoyloxyethyl)-fatty acid amide esters



United States Patent f 3,211,766 N-BIS(2-BENZOYLOXYETHYL)-FATTY ACIDAMIDE ESTERS Frank C. Magne, Robert R. Mod, and Evald L. Skau,

New Orleans, La., assignors to the United States of America asrepresented by the Secretary of Agriculture No Drawing. Originalapplication Oct. 24, 1961, Ser.

No. 147,377, now Patent No. 3,179,615, dated Apr. 20,

1965. Divided and this application Jan. 22, 1963, Ser. No. 263,369

2 Claims. (Cl. 260-404) (Granted under Title 35, US. Code (1952), sec.266) A non-exclusive, irrevocable, royalty-free license in the inventionherein described, throughout the world for all purposes of the UnitedStates Government, with the power to grant sublicenses for suchpurposes, is hereby granted to the Government of the United States ofAmerica.

This application is a division of Ser. No. 147,377, filed October 24,1961, now Patent No. 3,179,615.

This invention relates to a plastic composition, the plasticizercomponent of which is a novel class of amides. The amides which form theplasticizer component of the resinous composition which is subject ofthis invention have the ability to plasticize both the hydrophillic andthe hydrophobic type of resins and in addition are characterized bytheir ability to confer softening characteristics on nitrile rubbers.

It is known to prepare .amides of the type represented by the formulaare incompatible if R=R'=CH or if R R': a straight chain monoolefinichydrocarbon group such as C I-I We have found that compounds of thisformula are also incompatible if R'=CH and R is a long chain saturatedalkyl such as C H or if R=CH and R is a straight chain polyolefinichydrocarbon group such as C H .We have made the surprising discovery,however, that compounds of this formula are compatible if R=CH and R iseither a straight chain monoolefinic hydrocarbon group such as C H or along chain saturated or straight chain monoolefinic hydrocarbon groupcontaining at least one epoxy group such as C H O or C H O.

3,211,766 Patented Oct. 12, 1965 It is the object of this invention tosupply amides of the type represented by the formula wherein R is astraight chain hydrocarbon group of chain length C to C the straightchain hydrocarbon group being monoolefinic and/or epoxidized, i.e.,containing only one olefinic group and/or at least one epoxy group. Rmay also be phenyl, cyclohexyl, a substituted phenyl such as C H COOR",where R" represents a saturated alkyl group of less than about 9 carbonatoms.

It is also the object of this invention to supply mixtures of amidesrepresented by this formula consisting predominantly of diesteramides inwhich R represents a straight chain hydrocarbon group (or straight chainbydrocarbon groups) of chain length C to C these straight chainhydrocarbon groups being monoolefinic and/ or monoolefinic containing atleast one oxirane ring and/ or saturated containing at least one oxiranering, and R is a saturated alkyl group containing 3 or less carbonatoms.

These diesteramides are efficient primary solvent-type plasticizersexhibiting good compatibility with, and imparting long-term thermalstability, low volatility, and low brittle point to polymer andcopolymer compositions of vinyl chloride. The diesteramides are also,quite unexpectedly, efficient plasticizers for cellulose triacetate andin addition they possess utility as softeners for nitrile rubbers. Theterm vinyl chloride resins is used throughout this specification and theaccompanying claims to refer to polymers and copolymers of monomerscontaining vinyl chloride in a predominant proportion in parts byWeight. The term such as good compatibility, compatible, and compatibleplasticizers in reference to plasticizers for vinyl chloride resin areused throughout the specification to refer to plasticizers which show nosigns of exudation or migration to the surface for at least 30 days whenthe plasticizer is present in the proportion of about 60 parts per 100parts by weight of vinyl chloride resin.

The term long chain fatty acid is used through this specification andthe accompanying claims to refer to monocarboxylic aliphatic acidscontaining 12 or more carbon atoms.

The compatible diesteramides are primary plasticizers and act ascompatibilizers for incompatible diesteramides. For example, the binarycompositions where is composed of oleoyl-25% palmitoyl or epoxyoleoyll5%palmitoyl and in which R is CH are compatible, as are all proportions ofthese two binary mixtures. Ternary compositions can tolerate even largerproportions of palmitoyl than would be expected; e.g., the 30%palmitoyl35% epoxyoleoyl35% oleoyl mixture is fully compatible. Thus,mixtures of long chain fatty acids or esters can be used to preparecompatible diesteramides providing there is a predominance ofmonoolefinic, epoxy-saturated, or epoxymonoolefinic long chain fattyacids individually or in combination in the mixture. The fatty acidsobtained from cottonseed oil consist roughly of 27% of saturated (mostlypalmitic) acid, 27% of monounsaturated (oleic) acid, and 46% ofpolyunsaturated, linoleic) acid. The diesteramides prepared fromcottonseed oil acids are incompatible because of the large proportion ofsaturated and straight chain polyolefinic hydrocarbon groups in themixture. Compatible diesteramides can, however, be prepared fromcottonseed oil acids which have been modified either by converting thepolyunsaturated acyls in the mixture to monounsaturated acyls byselective hydrogenation, dimerization, halogenation and epoxidation orby converting the polyunsaturated acyls alone or both thepolyunsaturated and the monounsaturated acyls to saturated epoxyacyls.Similar adjustments in composition can be made in the fatty acidmixtures obtainable from other natural sources, such as vegetable oranimal oils and fats, tall oil, and the like, to prepare compatiblediesteramides. These adjustments of the degree of unsaturation may beperformed on the original oils, on the acids, on the esters, or on thediesteramides prepared from them. In general it is usually preferred toperform the epoxidation at the diesteramide stage.

The amides which are the subject of this invention we shall refer to asdiesteramides and they can be prepared as We shall show presently in avariety of ways. These diesteramides, which carry two substituent alkylgorups, e.g., two methyl groups and one substituent straight chainhydrocarbon group of chain length exceeding 11 carbon atoms whichsubstituent group may be monoolefinic and/ or epoxidized are, as notedabove, unexpectedly compatible with vinylchloride type resins. When thestraight chain hydrocarbon substituent is monoolefinic, completecompatibility with vinyl type resins exists up through chain lengths ofC Additionally, if the straight chain hydrocarbon substituent group isan epoxy-containing saturated or monoolefinic group, compatibility withvinyl chloride type resins extends through C chain lengths.

The diesteramides which are the subject of this invention can beprepared by the following sequential reactions. First, an alkanolaminesuch as diethanolamine is reacted with the alkyl ester, e.g., the methylester, of a long-chain fatty acid. This initial reaction is anester-exchange type of reaction and is carried out in the presence of analkoxide catalyst; e.g., sodium methoxide. If the alkanol amine used isdiethanolamine, a N-bis(2-hydroxyethyl) amide of a fatty acid is formed.The product of this first reaction is subsequently reacted with the acidanhydride or the acid chloride of an acid such as acetic, propionic,benzoic, hexahydrobenzoic acid, or of the monoester of dibasic acidssuch as phthalic or succinic acids or of the diesters of tribasic acidssuch as phosphoric acid. Acetic or benzoic acid is the preferred acid toesterify the two hydroxyl groups present. The diesteramides prepared bythe aforementioned sequence of reactions, we shall refer to assymmetrical diesteramides prepared by the directed method.

Other alkanolamines which may be used instead of diethanolamine aredialkanolamines such as di-isopropanolamine (l,l-imino-di-2-propanol),3,3'-iminodipropanol, and the like.

It is possible, alternatively, to prepare diesteramides by reactingsimultaneously all the components (the dialkanolamine and the two fattyacids of different chain lengths). The result of this alternativeprocess wherein all of the reaction components are present at the sametime in the reaction mixture produces what we shall refer to hereinafteras the mixed diesteramides produced by the undirected method. Since thereaction is a random one, the precise location of the varioussubstituents is not known and cannot be predicted with certainty as itcan with the directed reaction method. Mixed diesteramides couldpossibly contain all of the following diesteramides:

where X represents the moiety The following examples are set forth byway of illustration only and it will be understood that the inventlon isnot to be construed as limited by the details therein.

EXAMPLE 1.N*BIS Z-ACETOXYETHYL) OLEAMIDE Two hundred and ninety-sixgrams (1 mole) of methyl oleate was slowly added to a vigorously stirredmixture of 105 grams (1 mole) of diethanolamine and 3.6 grams (0.15moles) of metallic sodium dissolved in absolute methanol. The reactionwas carried out with continued stirring at 65 to 75 C. and at 60millimeters pressure. It is necessary to add the methyl oleate slowly soas to control frothing of the reaction mixture. The reaction wascomplete after all the methyl oleate had been added and the evolution ofmethanol had ceased. The product of this reaction was N bis(2hydroxyethyl)oleamide. To 124 grams (approximately 0.34 mole) ofN-bis(2-hydroxyethyl)oleamide from the above reaction was slowly addedwith stirring grams (0.78 mole) of acetic anhydride. The reactiontemperature was maintained at 70 to 75 C. during and for an additional30 minutes subsequent to the addition of the acetic anhydride. Thereaction product was taken up in commercial hexane, washed free ofacetic acid with water, and stripped of hexane. Analysis of the strippedproduct showed 3.09% nitrogen. The theoretical nitrogen content forN-bis(2- acetoxyethyl)oleamide is 3.09%. This material was tested as aplasticizer for vinyl chloride resin (see Sample No. 1A in Table I).

A separate fraction of the diesteramide prepared as above was distilledin a short-path still at 0.3 millimeters pressure and a small fractionboiling at 188 C. was rejected. The main distillation-cut, boiling atabout 219 C., was tested as a plasticizer for vinyl chloride resin (seeSample No. 1B in Table I).

EXAMPLE 2.N-BIS(2-BENZOYLOXYETHYL)- OLEAMIDE To 35 grams (0.10 mole) ofN-bis(2-hydroxyethyl)- oleamide, prepared as shown in Example 1 andisolated from the reaction mixture by the addition of a silght excess ofglycolic acid followed by extraction with hexane, washing and stripping,was added 30.8 grams (0.22 mole) of benzoyl chloride. The reaction wascarried out in 35 grams of benzene. The temperature was raised slowlyand maintained at 80 C. for two hours following which time 17.3 grams(0.22 mole) of pyridine was added. The temperature was then raised to 98C., held for one hour, and the reaction mixture then allowed to cool.The reaction product was isolated from this mixture by washing withwater, and with aqueous sodium carbonate, and finally stripped to removethe benzene. The product N- bis(2-benzoyloxyethyl)oleamide, had anitrogen content of 2.40% (theory 2.43). The product was tested as avinyl chloride resin plasticizer (see Sample No. 2 in Table I).

EXAMPLE 3 .-N-BIS 2-ACETOXYETHYL) LINOLEAMIDE This material was preparedby the method of Example 1, substituting methyl linoleate for the methyloleate. The isolated product gave a nitrogen analysis of 2.87% (theory3.10%). It was tested as a vinyl chloride resin plasticizer (see SampleNo. 3 in Table I).

EXAMPLE 4.-N-BIS Z-ACETOXYETHYL) AMIDE OF COTTONSEED OIL FATTY ACIDSThis material was prepared by the method of Example 1, using the methylesters of cottonseed oil fatty acids 5 instead of methyl oleate. (Themethyl esters were derived from cottonseed oil fatty acids having aniodine value (I.V.) of 113 and a neutralization equivalent of 273.) Theproduct gave a nitrogen analysis of 3.10% (theory 3.15%). It was testedas a plasticizer for vinyl chloride resin (see Sample No. 4 in Table I).

EXAMPLE 5.N BIS(2 ACETOXYETHYL)AMIDE OF SELECTIV ELY HYDROGENATEDCOTTON- SEED OIL FATTY ACIDS This material was prepared by the method ofExample 1 using the methyl esters of selectively hydrogenated cottonseedoil fatty acids instead of methyl oleate. (The selectively hydrogenatedcottonseed oi'l fatty acids had an I.V. of 73.2, a thiocyanogen value of68.0, and a neutralization equivalent of 274.) The product had an I.V.of 44.9 and gave a nitrogen analysis of 3.05% (theory 3.14% It wastested as a vinyl chloride resin plasticizer (see Sample No. 5 in TableI).

The product, N-bis(2-acetoxyethyl)amide of the hydrogenated cottonseedacids, was tested as a plasticizer for cellulose triacetate (41%acetyl). This composition, cast as a film from a mixture of 30 parts ofdiesteramide and 100 parts of cellulose triacetate in acetone solvent,was flexible, clear, nongreasy, and withstood repeated flexing along asharp crease without cracking. This is a compatible composition.

EXAMPLE 6.-N-BIS (Z-ACETOXYETHYL) EP OXY- OLEAMIDE 0.077 mole of theproduct from Example 3 was dissolved in 50 grams of chloroform and addedslowly to 192 grams of a chloroform solution of perbenzoic acid,containing 11.7 grams (0.085 mole) of perbenzoic acid, while maintaininga temperature of to 5 C. The reaction mixture was allowed to stand at 0C. for 24 hours. The N-bis(2-acetoxyethyl)epoxyoleamide was extractedwith a volume of diethyl ether equal to two times that of the reactionmixture. The extract was washed free of any benzoic acid, and the etherstripped off. The product had a nitrogen content of 2.73% (theory 2.99%)and an oxirane-oxygen content of 3.74% (theory 3.42%). It was tested asa plasticizer for vinyl chloride resin (see Sample No. 6 in Table I).

EXAMPLE 7.N BIS(2 ACETOXYETHYL)AMIDE OF PARTIALLY EPOXIDIZED COTTONSEEDOIL FATTY ACIDS 60 R FREEBERG 31910 NITE PATS SEPT 22 The product ofExample 4 was partially epoxidized with perbenzoic acid by the processdescribed in Example 6. In this instance the ratio of perbenzoic acid toamide was 0.056 to 0.077 mole. The oxirane-oxygen content of the productwas 2.35%. The product was tested as a plasticizer for vinyl chlorideresin (see Sample No. 7 in Table I).

EXAMPLE 8.-N BIS(2-ACETOXYETHYL)AMIDE OF COMPLETELY EPOXIDIZED RAPESEEDFAT- TY ACIDS The N-bis(2-acetoxyethyl)amide of rapeseed acids wasprepared by the method of Example 1 except that the methyl esters ofrapeseed fatty acids were used in place of methyl oleate. This producthad an I.V. of 73.8 and a nitrogen content of 2.69% (theory 2.94%). Itwas evaluated as a vinyl chloride resin plasticizer and found to beincompatible. It. was epoxidized by the procedure of Example 7 to anoxirane content of 3.93% using 1.3 moles of perbenzoic acid per mole ofamide. The epoxidized product was tested as a vinyl chloride resinplasticizer (see Sample No. 8 in Table I).

6 EXAMPLE 9.-MIXED DIESTERAMIDES (UNDI- RECTED PROCESS) OF SELECTIVE'LYHYDRO- GENATED COTTONSEED OIL ACIDS AND ACE- TIC ACID 0.20 mole ofdiethanolamine, 0.40 mole of glacial acetic acid, 0.205 mole of theselectively hydrogenated cottonseed acids described in Example 5, and 25ml. of benzene were refluxed in an oil bath at a temperature of 200 C.until there was no further evolution of water. (This was ascertained byobserving the water collected in the Dean- Stark trap.) The reactionproduct was cooled, dissolved in commercial hexane, washed to removediethanolamine or acetic acid, dried, percolated through a column ofactivated alumina, and the hexane stripped off. This product gave anitrogen analysis of 3.09% (theory 3.14%). It was tested as a vinylchloride resin plasticizer (see Sample No. 9 in Table 1).

EXAMPLE 10.-MIXED DIESTERAMIDES OF OLEIC AND ACETIC ACIDS The sameprocedure and the same molar proportions of reactants were used as inExample 9, except that oleic acid was used instead of the hydrogenatedcottonseed acids. This product gave a nitrogen analysis of 2.71% (theory3.09%). It was tested as a vinyl chloride resin plasticizer (see SampleNo. 10 in Table 1).

EXAMPLE 11.MIXED DIESTERAMIDES OF EPOX- IDIZED COTTONSEED OIL ACIDS ANDACETIC ACID The same procedure and the same molar proportions ofreactants were used as in Example 9 except that the cottonseed oil fattyacids described in Example 4 were used instead of the hydrogenatedcottonseed oil fatty acids. This product gave a nitrogen analysis of2.73% (theory 3.14%). It was partially epoxidized using the same processand molar proportions of amide and perbenzoic acid as shown in Example7. The end product had an oxirane-oxygen content of 1.58%. It was testedas a vinyl chloride resin plasticizer (see Sample No. 11 in Table I).

The various diesteramides were tested as plasticizers for vinylchloride-vinyl acetate (95.5) copolymer resin (Vinylite VYDR) in thefollowing formulation:

Percent Vinyl chloride resin 63.5 Diesteramide 35.0 Stearic acid 0.5Basic lead carbonate 1.0

This formulation for each diesteramide sample was milled, molded, andtested. The results are shown in Table 1, Examples 1 through 11. In allexamples the sample was rated incompatible if the molded stock showedany evidence of exudation or migration to the surface during a shelfstorage of 30 days.

The following formulation were used to test the diesteramides assofteners for nitrile rubber (Hycar 104233% acrylonitrile) Parts Nitrilerubber 100.0 SRF black 60.0 Zinc oxide 5.0 Stearic acid 1.5 Sulfur 1.5Benzothiazyldisu'lfide 1.5 Softener 20.0

These compositions were cured for 30 minutes at 310 F. TheN-bis(2-acetoxyethyl) amides of the hydrogenated and partiallyepoxidized cottonseed oil acids (prepared in Eaxmples 5 and 7,respectively, were found to be acceptable in compatible softeners fornitrile rubber,

showing no signs of spewing in 30 days. The test results for thesecompositions are shown as Samples 5 and 7, respectively, in Table II.

wherein R is a straight-chain monoolefinic hydrocarbon Table I Tensile100% Elonga- Brittle Vola- Sample No. strength, modution, point, tilityCompatip.s.i. lus percent C bility "p.s.i.

2,810 1, 620 310 o 3, 090 l, 670 320 C 3, 700 2, 500 270 1G I 3, 060 1,e50 370 c 1 0 3, 280 1, 450 370 C 2, 910 1, 620 290 C 3, 390 1, 970 2900 2, 510 1, 810 250 C 2, 740 1, 750 290 o 3, 070 1, 630 390 C 15 grouphaving from 11-17 carbon atoms.

* C=compatible; I=incompatible.

2. N-bis(Z-benzoyloxyethyl)oleamide.

Table II Tensile Strength Elongation 300% Modulus Shore A Weight BrittleVolume Sample No. Hardness, 1058, point, change, Unuged, Aged, Unaged,Aged, Unaged, Aged, 10 see. percent C. percent p.s.i. p.s.i. percentpercent p.s.i. p.s.i.

References Cited by the Examiner Ciba, CA, 43, 1949, page 4878gh.

CHARLES E. PARKER, Primary Examiner.

1. A COMPOUND REPRESENTED BY THE FORMULA